Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
  • C23C22/08—Orthophosphates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment

Definitions

• the invention is in the field of anti-corrosion treatment of metal surfaces.
• One aspect of the invention is to deposit a corrosion-protective layer on the bare metal surface.
• a second aspect of the invention consists in enhancing the anti-corrosion effect of an anti-corrosion layer already deposited on the metal surface.
• a special feature of the invention is that no toxic heavy metals such as chromium or nickel have to be used.
• conversion treatment means that components of the treatment solution react chemically with the metal surface, thereby creating a corrosion protection layer in which both components of the treatment solution and metal atoms from the metal surface are incorporated.
• US-A-5 129 967 discloses treatment baths for a no-rinse treatment (referred to there as “dried in place conversion coating") containing aluminum a) 10 to 16 g / l polyacrylic acid or its homopolymers, b) 12 to 19 g / l hexafluorozirconic acid, c) 0.17 to 0.3 g / l hydrofluoric acid and d) up to 0.6 g / l hexafluorotitanic acid.
• a no-rinse treatment referred to there as “dried in place conversion coating”
• aluminum a) 10 to 16 g / l polyacrylic acid or its homopolymers, b) 12 to 19 g / l hexafluorozirconic acid, c) 0.17 to 0.3 g / l hydrofluoric acid and d) up to 0.6 g / l hexafluorotitanic acid.
• EP-B-8 942 discloses treatment solutions, preferably containing aluminum cans
• DE-C-19 33 013 discloses treatment baths with a pH above 3.5 which, in addition to complex fluorides of boron, titanium or zirconium, in amounts of 0.1 to 15 g / l, based on the metals, additionally 0.5 up to 30 g / l of oxidizing agents, especially sodium metanitrobenzenesulfonate.
• DE-C-24 33 704 describes treatment baths to increase paint adhesion and permanent corrosion protection to, among other things.
• Aluminum which can contain 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as Zr ⁇ 2. The pH values of this
• a molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10 must be observed.
• DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans which contain at least 10 ppm titanium and / or zirconium, between 10 and 1000 ppm phosphate and a sufficient amount of fluoride to form complex fluorides of the titanium and / or zirconium present however, contain 13 ppm and have pH values between 1, 5 and 4.
• WO 92/07973 teaches a chromium-free treatment process for aluminum, which as essential components in acidic aqueous solution 0.01 to about 18 wt .-% H 2 ZrF 6 and 0.01 to about 10 wt .-% of a 3- (N- C ⁇ -4 alkyl-N-2-hydroxyethylaminomethyl) -4hydroxystyrene polymer used.
• Optional components are 0.05 to 10% by weight of dispersed SiO 2 , 0.06 to 0.6% by weight of a solubilizer for the polymer and surfactant.
• this invention relates to a method for the corrosion protection treatment of a metal surface, which is characterized in that the metal surface is brought into contact with a homo- or copolymer of vinylpyrrolidone.
• the metal surface can first be subjected to a conversion treatment according to the prior art, for example zinc or iron phosphating, a conversion treatment with fluoro acids of metals, for example titanium, zircon or hafnium or also of boron or silicon, or treatment with a solution or suspension of an organic polymer containing no vinyl pyrrolidone units.
• a conversion treatment for example zinc or iron phosphating
• fluoro acids of metals for example titanium, zircon or hafnium or also of boron or silicon
• treatment with a solution or suspension of an organic polymer containing no vinyl pyrrolidone units are mentioned in the literature cited at the beginning.
• An alternative embodiment of the cited invention is that the metal surface is brought into contact with a homo- or copolymer of vinyl pyrrolidone while it is being subjected to a conversion treatment.
• a homo- or copolymer is therefore present in the treatment solution with which a conversion layer is generated on the metal surface.
• the treatment solution for producing the conversion layer can contain, for example, phosphoric acid or its anions.
• divalent cations such as zinc and / or manganese can be present in the treatment solution.
• a particular example of such a treatment solution for producing a conversion layer is a zinc phosphating solution which produces a crystalline layer of zinc-containing metal phosphates on the metal surface.
• the treatment solution can also contain phosphoric acid and / or its anions, but not divalent metals.
• An example of this is an iron phosphating solution which produces an essentially non-crystalline layer of metal phosphates and / or metal oxides on a metal surface, in particular an iron-containing surface.
• the presence of homo- or copolymers of vinylpyrrolidone in such a treatment solution improves the corrosion protection caused by the conversion layer is achieved. This also applies if the treatment solution contains, in addition to homopolymers or copolymers of vinylpyrrolidone, as the conversion layer-forming component, fluoric acids and / or complex fluorides of metals and semimetals, such as boron, silicon, titanium, zirconium and / or hafnium.
• the ready-to-use solution for the treatment of metal surfaces preferably contains between 0.05 and 200 g / l of a homo- or copolymer of vinylpyrrolidone.
• the object of the present invention is to improve the subject matter of DE 100 05 113 with regard to the efficiency of the use of chemicals.
• the present invention relates to an agent for the treatment of metal surfaces which contains phosphoric acid and / or at least one fluoric acid of one or more elements from the group Zr, Ti, Hf and Si or in each case their anions and a homo- or copolymer of vinylpyrrolidone, characterized in that it is available as a ready-to-use solution containing a) 0.02 to 20 g / l phosphoric acid and / or at least one fluoro acid of one or more elements from the group Zr, Ti, Hf and Si or their respective anions and b) 10 to 49.9 mg / l of a homo- or copolymer of vinyl pyrrolidone contains.
• the agent for treating metal surfaces is a phosphating solution. If it does not contain ions of divalent metals such as zinc and / or manganese, it is present as a so-called "non-layer-forming" phosphating solution, for example in the form of an iron phosphating solution.
• Zinc and / or manganese Phosphating solutions containing, for example, 0.3 to 2 g / l of zinc ions and, if desired, additionally or instead of about the same concentration of manganese ions, are known in the conversion treatment field as so-called “layer-forming” phosphating solutions.
• the treatment solution can also contain one or more fluoro acids of one or more elements from the group Zr, Ti, Hf and Si contain.
• both phosphoric acid and the above-mentioned fluoroacids are present in the form of one or more negatively charged anions.
• the ratio of acid anions to undissociated acid depends on the protolysis constant of the respective acid and on the pH currently set. This phenomenon is commonly known as acid-base balance.
• the agents contain water and, if desired, further active ingredients or auxiliaries for adjusting the pH, for increasing the corrosion protection effect, for improving the applicability and possibly for other purposes.
• these copolymers can contain one or more other monomers in addition to vinyl pyrrolidone.
• Mixtures of homo- and two-component copolymers, homo- and terpolymers or two-component copolymers and terpolymers can also be used.
• the ready-to-use agent can be obtained by diluting a concentrate which is the subject of the unpublished German patent application DE 100 05 113.
• a concentrate which is the subject of the unpublished German patent application DE 100 05 113.
• it may be the case that concentrates which already contain all the active ingredients are not stable in storage for a sufficiently long time.
• one component of the concentrate contains at least predominantly the inorganic components of the agent, while at least one other component of the concentrate contains the organic polymers.
• the two components of the concentrate can then have different pH values, as a result of which the storage stability of the concentrate components can be increased.
• the individual components of the concentrate are included Diluted water so far that the active ingredients are in the desired concentration range. It may be necessary to adjust the pH to the desired range by adding an acid or a base.
• Preferred concentration ranges for the active substances a) and b) in the application solution are: in the case of phosphoric acid or phosphate ions 5 to 20 g / l, in particular 8 to 16 g / l phosphate ions, in the case of fluoric acids such an amount that Zr, Ti , Hf and / or Si, based on these elements, are present in a concentration in the range between 20 and 1,000 mg / l, in particular 50 to 400 mg / l.
• the concentration of the polymers or copolymers of vinylpyrrolidone in the application solution is preferably in the range from 20 to 45 mg / l.
• Suitable homopolymers or copolymers of vinylpyrrolidone are, for example, the polymers listed in Table 1 or the polymers of the monomers listed therein.
• the agents according to the invention can contain further transition metal ions such as, for example, ions of the elements zinc, manganese, cerium or vanadium or also hydrofluoric acid or free fluorides.
• transition metal ions such as, for example, ions of the elements zinc, manganese, cerium or vanadium or also hydrofluoric acid or free fluorides.
• chromium or nickel ions can also offer advantages in principle. For reasons of work and environmental protection, however, the addition of chromium or nickel ions is preferably avoided. Accordingly, there is a preferred embodiment of the invention in that the agent is free of nickel and chromium. This means that these metals or their compounds are not intentionally added to the agent.
• the concentrations of nickel and / or chromium in the ready-to-use treatment solution will be no higher than about 10 ppm.
• the ready-to-use agent according to the invention preferably has a pH in the range from 1 to 6 and in particular in the range from 2 to 5.5.
• acid-soluble compounds of Zr, Ti, Hf or Si as well as hydrofluoric acid or soluble fluorides can be added separately, since the fluoroanions of the elements mentioned form from this.
• the pH must be adjusted to the desired range by adding acid such as the free fluoric acids of the elements mentioned, but also, for example, hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid or by adding a base such as alkali metal carbonate solution, alkali metal hydroxide solution or ammonia.
• acid such as the free fluoric acids of the elements mentioned, but also, for example, hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid
• a base such as alkali metal carbonate solution, alkali metal hydroxide solution or ammonia.
• composition according to the invention contains, in a special embodiment, homopolymers or copolymers of vinylpyrrolidone which contain caprolactam groups.
• metal surfaces can, for example be selected from surfaces of steel, galvanized steel (electrolytically or hot-dip galvanized), alloy-galvanized steel, aluminum or magnesium.
• the metals aluminum and magnesium are usually not in pure form, but as alloys with other elements such as lithium, zinc, copper, silicon, magnesium (in the case of aluminum alloys) or aluminum (in the case of magnesium alloys).
• the method is designed for the treatment of surfaces of such metals, which are used in vehicle construction, in the household appliance industry, in the architecture or furnishing sector.
• Metal surfaces that do not yet have a corrosion protection layer can be treated.
• the treatment method according to the invention then produces a corrosion-protective coating which at the same time improves the adhesion of an organic coating, such as a varnish, which may be applied later.
• metal surfaces which already have a pre-formed corrosion protection layer can also be treated with the method according to the invention. In this case, the corrosion protection effect of this already applied corrosion protection layer is further improved.
• the method according to the invention is suitable for the aftertreatment of metal surfaces which have an X-ray amorphous or crystalline coating, as are produced, for example, by non-layer-forming or layer-forming phosphating, for example layer-forming zinc phosphating.
• the treatment according to the invention of such pretreated metal surfaces leads to the fact that pores remaining in the pretreatment are closed in the first corrosion protection layer.
• the metal surfaces can be brought into contact with the treatment solution, for example by spraying or immersion.
• the treatment solution with the metal surface in the so-called No-rinse process can be brought into contact.
• the treatment solution is either sprayed onto the metal surface or transferred onto the surface by application rollers. This is followed by drying of the treatment solution without further intermediate rinsing, after an exposure time which can be, for example, in the range from 2 to 20 seconds. This can be done, for example, in a heated oven.
• the treatment solution preferably has a pH in the range from 1 to 6, with narrower pH ranges being preferred depending on the substrate and type of application and duration of action.
• the pH is preferably set to the range from 2 to 6, and in the case of treatment of aluminum surfaces in particular to the range from 2 to 4; when treating steel, zinc or galvanized steel, in particular in the range from 3 to 5.
• Metal surfaces which have already been pretreated and which carry a phosphate layer, for example, are preferably brought into contact with a treatment solution with a pH in the range from 3.5 to 5.
• the temperature of the treatment solution when carrying out the method according to the invention can generally be between the freezing point and the boiling point of the treatment solution, with temperatures in the region of room temperature or above being preferred for practical reasons.
• the treatment solution can have a temperature in the range from 15 to 60 ° C. and in particular from 20 to 45 ° C.
• the treatment method according to the invention represents a partial step in a sequence of method steps that is otherwise customary in the area concerned.
• the metal surfaces to be treated are usually cleaned with a conventional cleaning solution before the treatment according to the invention.
• the cleaning step can be omitted if the metal surfaces to be treated were coated, for example galvanized, immediately before the treatment according to the invention, or if they were subjected to a conversion treatment, for example phosphating.
• the metal surfaces usually provided with an organic coating, for example a lacquer. This can be, for example, a powder coating or an electrolytically, in particular cathodically, immersible coating.
• a sequence of processes which is particularly preferred when using the process according to the invention is that the metal surface is treated with an aqueous solution of an acid before it is brought into contact with the agent described above to produce a conversion layer, that is to say during a conversion treatment.
• the preceding process step of treating the metal surface with an aqueous solution of an acid before the conversion treatment is also referred to in the art as "acid pickling” or "pickling passivation”.
• acids can be used for this purpose, which are usually used for acidic pickling or pickling passivation.
• An example of this is phosphoric acid.
• Hot-dip galvanized steel HDG
• electrolytically galvanized steel EG
• aluminum AC120
• cold-rolled steel CRS
• Vinyl pyrrolidone / vinyl caprolactam polymer (37 mg / l solid)
• Example 2 Process sequence as above but without steps 3 and 4.
• Zinc-coated substrates paint adhesion after salt water storage
• Example 3 Conversion process with subsequent powder coating (galvanized steels) with copolymer mixtures
• Example 4 Conversion Process with Copolymer Mixtures (Powder Coating)

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Treatment Of Metals (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)

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Publications (2)

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• 2001
  • 2001-06-30 DE DE10131723A patent/DE10131723A1/de not_active Withdrawn
• 2002
  • 2002-06-21 CZ CZ20033572A patent/CZ20033572A3/cs unknown
  • 2002-06-21 SK SK1619-2003A patent/SK16192003A3/sk unknown
  • 2002-06-21 CN CNA028132149A patent/CN1527889A/zh active Pending
  • 2002-06-21 EP EP02780906A patent/EP1402083B1/fr not_active Expired - Lifetime
  • 2002-06-21 DE DE50202924T patent/DE50202924D1/de not_active Expired - Fee Related
  • 2002-06-21 AT AT02780906T patent/ATE294259T1/de not_active IP Right Cessation
  • 2002-06-21 CA CA002453138A patent/CA2453138A1/fr not_active Abandoned
  • 2002-06-21 KR KR10-2003-7017270A patent/KR20040043135A/ko not_active Application Discontinuation
  • 2002-06-21 BR BR0210725-2A patent/BR0210725A/pt not_active IP Right Cessation
  • 2002-06-21 MX MXPA03011369A patent/MXPA03011369A/es unknown
  • 2002-06-21 RU RU2004102694/02A patent/RU2004102694A/ru not_active Application Discontinuation
  • 2002-06-21 JP JP2003508743A patent/JP2004533542A/ja active Pending
  • 2002-06-21 WO PCT/EP2002/006888 patent/WO2003002781A1/fr active IP Right Grant
  • 2002-06-21 ES ES02780906T patent/ES2240824T3/es not_active Expired - Lifetime
• 2003
  • 2003-12-11 US US10/734,815 patent/US20040151619A1/en not_active Abandoned

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